Waterborne film-forming compositions containing reactive surfactants and/or humectants

ABSTRACT

The present invention is directed to aqueous coating compositions, such as paints, containing a film-forming latex polymer and a reactive surfactant and/or a low VOC humectant. The reactive surfactant, a polyglycerol ester or ether of an unsaturated fatty acid, reduces or eliminates the need for traditional water-soluble additives that lower the water resistance of the dry coating. Additionally, the reactive surfactants of the invention are capable of oxidative cross-linking during the curing process, forming a dry film that is more durable and water-resistant than traditional latex paint composition. The low VOC humectant polyglycerol, isosorbide, or a derivative of isosorbide can replace at least in part traditional humectants such as propylene glycol which contribute to VOCs, while maintaining an effective open time for application of the aqueous coating compositions.

RELATED APPLICATIONS

This application is a divisional application of prior, co-pending U.S.application Ser. No. 12/259,795, filed Oct. 28, 2008, which itselfclaims the benefit under 35 U.S.C. §119(e) of U.S. ProvisionalApplication Ser. No. 60/000,918, filed Oct. 30, 2007, the contents ofthe entirety of which are incorporated by this reference.

FIELD OF THE INVENTION

The invention is directed to aqueous film-forming compositionscontaining a reactive surfactant and/or a humectant.

BACKGROUND OF THE INVENTION

Water-based latex paint is generally composed of an aqueous dispersionof pigments and latex particles that impart substrate hide, waterresistance, and durability to the solid paint film. Other componentssuch as dispersants, surfactants, and thickeners can be added to theliquid paint to maintain a stable dispersion and suspension of thepigments and latex particles. Solvents, bases, defoamers, and biocidescan also be incorporated to improve liquid stability, applicationperformance and film formation properties.

The chemical composition of water-based latex paints is designed toallow dispersion of components in water, yet maintain water resistanceupon curing and forming a dry paint film. Essentially, the compositionsare designed to contain a hydrophobic component for water resistance asa paint film, and a hydrophilic component to improve stability,solubility, and dispersion in the liquid aqueous phase.

Latex polymers are the film-forming portions of the paint film, and areprepared by an emulsion polymerization reaction. Aggregation of polymerparticles is typically discouraged by including a stabilizing surfactantin the polymerization mix. In general, the growing latex particles arestabilized during emulsion polymerization by one or more surfactantssuch as an anionic or nonionic surfactant, or a mixture thereof.Examples of surfactants suitable for emulsion polymerization are givenin McCutcheon's Detergents and Emulsifiers (MC Publishing Co., GlenRock, N.J.) (2007 ed.). Generally, emulsion polymerization includes useof nonionic surfactants to create monomer micelles within the waterphase.

Water-borne paint and coating formulations are among the most complexsystems in surface and colloid chemistry. Surfactants are needed toreduce the free energy of the various interfaces of the system, therebykinetically stabilizing these paint formulations. Commonly, surfactantsare used as binder emulsifiers and as pigment dispersants. Additionally,surfactants are added to paint and coating formulations to improvewetting on low energy substrates, to control foaming during applicationand processing, and to prevent film defects caused by surface tensiongradients. Handbook of Applied Surface and Colloid Chemistry, p. 105,Holmberg, K. (2001).

Nonionic surfactants, nonionic and anionic dispersants, nonionicthickeners, anionic alkali swellable thickeners, and water solublecellulosic thickeners can be used in paint and coating compositions toseparate, suspend and stabilize latex particles and pigment particles.Generally, the structures of these paint components contain ahydrophobic functionality synthetically combined with a hydrophilicfunctionality. Inorganic pigments are relatively heavy particles thatwould agglomerate and settle at the bottom of a container of latex paintwithout the use of anionic surfactants as well as various dispersantsand thickeners for suspension.

Typically, surfactants, thickeners and dispersants are generally lowermolecular weight components that remain in the paint film, which cansignificantly reduce water resistance and durability of the paint film.These components are required to maintain stability in the aqueous phasefor in-can storage, but can compromise the end use function of a paintfilm.

In contrast to latex compositions, oil-based compositions, e.g.,oil-based paints, commonly employ vegetable oils such as linseed oil ortung oil and/or vegetable oil co-reacted with other compounds (such asalkyd resins) as a component of the vehicle in the paint. The vegetableoils, which are also referred to in the art as “drying oils”, formcrosslinked films upon exposure to air. Like all vegetable oils, thesedrying oils are triesters of various fatty acids and glycerol (i.e.“triglycerides” or “triacylglycerols”). However, unlike most vegetableoils, the fatty acids in drying oils have a very high degree ofunsaturation (high iodine value), are high in polyunsaturated fattyacids, and generally have a majority of fatty acids that contain 3 ormore double bonds (such as, for example linolenic[cis-9-cis-12-cis-15-Octadecatrienoic]acid, eleostearic[cis-9-trans-11-trans-13-Octadecatrienoic]acid, and4-Oxo-cis-9-trans-11-trans-13-Octadecatrienoic acid). Semi-drying oilshave moderate to high degrees of unsaturation, and are high inpolyunsaturated fatty acids, but contain lower levels of fatty acidsthat have 3 or more double bonds.

The use of such reactive drying oils in oil-based paint helps to providea paint film which is hard and durable. Thus, the drying oils andco-reacted vegetable oil products (alkyds) are desirable components ofoil-based compositions. However, oil-based compositions typicallycontain large proportions of volatile organic compounds (“VOC's”) assolvents or additives, e.g., 380 to 450 grams per liter (“g/l”) or more.Such high concentrations of VOC's are environmentally undesirable.

Latex compositions, on the other hand, typically contain lowerconcentrations of VOC's, e.g. less than about 250 g/l and thus are moreenvironmentally compatible. Accordingly, it would be desirable toincorporate the drying oils of oil-based compositions into latexcompositions to promote crosslinking of the latex compositions. However,the drying oils used in oil-based compositions are not water-soluble andaccordingly cannot readily be used in latex compositions.

It would also be desirable to develop a latex paint formulation whichincorporates components that can react during the curing process, andthereby help form a durable, water-resistant paint film. It wouldfurther be desirable to reduce the amounts of the water-soluble orwater-sensitive components which provide emulsifying and rheologicproperties in the can but also can contribute to poorer properties ofthe dry coating.

U.S. Pat. No. 6,924,333 (“the '333 patent”) discloses a latex paintcomposition comprising polyunsaturated fatty acid-containing additivesderived from vegetable oils. In one aspect, the '333 patent discloses alatex paint composition comprising a latex polymer and a polyunsaturatedfatty acid moiety chemically attached to a glycol or a polyol through anester, ether, or urethane linkage. The '333 patent further disclosesthat in a preferred embodiment, the glycol is ethylene glycol,diethylene glycol, 1,4-butanediol, propylene glycol, or 1,3-propanediol.

Although the compositions disclosed in the '333 patent may be suitablefor particular latex compositions, it would be desirable to developadditional latex compositions having components that can react duringthe curing process and thereby help form a durable, water-resistantpaint film.

Another component typically found in aqueous coating compositions, suchas latex paints, is a humectant. A humectant is usually added to serveas both an antifreeze agent and to control the rate of evaporation fromthe coating film. Ethylene glycol is most commonly used, followed bypropylene glycol.

As an antifreeze, the glycol depresses the freezing point of the aqueousmedium. As water freezes, its volume expansion can push the latexparticles together with sufficient force to cause coagulation byovercoming the stabilizing dispersant/surfactant layer. With a glycoladded, even those paints or other coatings which become cold enough tofreeze tend to freeze to a slush that exerts less force on the latexparticles.

As a humectant, the glycol controls evaporation from the paint film tofacilitate wet lapping. When paint is applied by roller or brush, eachbrush-full or roller-full of paint overlaps the wet edge of thepreceding area of coverage. Without the glycol, evaporation can quicklyleave the previously applied film edge very viscous, although very weakdue to only limited latex coalescence. The brush or roller shear fromthe subsequent lapped application can break up this film, leavingirregularities along the lapped edge (Ciullo, P. A., Industrial Mineralsand Their Uses—A Handbook and Formulary William Andrew Publishing/Noyes(1996)).

Although ethylene glycol and propylene glycol are suitable humectantsfor latex paints and other coatings, they contribute to VOC's. As VOC'sare generally considered to be environmentally detrimental, it would behighly desirable to substitute ethylene glycol and propylene glycol atleast in part with lower- or zero-VOC humectants in aqueous coatingcompositions.

BRIEF SUMMARY OF THE INVENTION

In one embodiment, the invention is directed to an aqueous coatingcomposition comprising one or more film-forming latex polymers and areactive surfactant. The reactive surfactant comprises one or morepolyglycerol derivatives chosen from or selected from the groupconsisting of a polyglycerol ester and a polyglycerol ether of one ormore unsaturated fatty acids.

The polyglycerol esters and ethers of polyunsaturated fatty acids reduceor eliminate the need for traditional water-soluble additives that lowerthe water resistance of the dry coating (e.g. paint) film. Thesereactive surfactants can replace petroleum-based derivatives such asnonylphenol ethoxlates (NPEs), which have faced much scrutiny for theirlong term environmental impact on water supplies and aquatic life.

Additionally, the polyglycerol esters and ethers of polyunsaturatedfatty acids are capable of oxidative crosslinking during the curingprocess, forming a dry paint film that is more durable andwater-resistant than traditional latex paint compositions. Furthermore,these moieties have good functionality, do not contribute to VOCs, andcan be advantageously used in conjunction with and interact with otherpolyunsaturated components in a latex formulation such as reactivecoalescents, reactive thickeners, and resins that include reactive sitessuch as acetoacetate functionality.

In another embodiment, the invention is directed to an aqueous coatingcomposition comprising one or more film-forming latex polymers and ahumectant. The humectant comprises one or more polyglycerols.Alternatively, the humectant may comprise isosorbide and/or a derivativethereof.

Polyglycerols, isosorbide, and derivatives of isosorbide can serve aszero-VOC humectants to help reduce levels of glycols such as propyleneglycol in latex paints and other coatings to control evaporation andmaintain open time.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a comparison of adhesion of a high gloss interior/exteriorwhite paint formulation containing isosorbide versus propylene glycol asa humectant, in accordance with Example 6.

DETAILED DESCRIPTION OF THE INVENTION

In one embodiment, the invention is directed to an aqueous coatingcomposition comprising one or more film-forming latex polymers and areactive surfactant. The reactive surfactant comprises one or morepolyglycerol derivatives chosen from or selected from the groupconsisting of a polyglycerol ester and a polyglycerol ether of one ormore unsaturated fatty acids.

Another embodiment of the invention is directed to aqueous coatingcompositions containing a humectant having a reduced VOC contentcompared to those containing ethylene glycol or propylene glycol. Theaqueous coating composition comprises (a) one or more film-forming latexpolymers and (b) a humectant comprising one or more polyglycerols.Alternatively, the aqueous coating composition comprises (a) one or morefilm-forming latex polymers and (b) a humectant comprising isosorbide ora derivative thereof.

As used herein, the term “aqueous coating composition” is intended toencompass compositions containing an aqueous phase (e.g., water) thatare applied to substrates. Illustrative coatings that can utilize thecomposition of the invention include wood coatings such as, e.g.,stains, seal coat/sealers, topcoats, wiping stains, glazes, and fillers.Examples of other coatings include paints (e.g., house paints), primers,clear coatings, semi-gloss coatings, gloss coatings, architecturalcoatings, industrial coatings, maintenance coatings, general metal-typecoatings, paper coatings including textile treatments, plastics coatingssuch as primers, base coats, top coats, and adhesion promoters, andpolishes.

Other suitable types of coatings that are embodied by the aqueouscoating compositions of the invention can be found in “Paint & InkFormulations Database” by Earnest W. Flick, 2005; WilliamAndrew—publisher; ISBN: 0815515081; Paint and Surface Coatings: Theoryand Practice, 2nd Ed. by R. Lambourne and T. A. Strivens, eds., 1999;William Andrew—publisher; ISBN: 18884207731; and “Organic Coatings:Science and Technology, 2nd Ed; by Zeno W. Wicks et al., 1999;Wiley-Interscience; ISBN:0471245070, all incorporated by referenceherein.

A “latex polymer” or “film-forming latex polymer” (used interchangeablyherein) refers to a high molecular weight, film-forming component whichimparts water resistance and durability to the dry coating film.Suitable latex polymers include polymerization and co-polymerizationproducts of vinyl acetate, acrylic acid, methacrylic acid, styrene,alpha-methyl styrene, butadiene, acrylates, methacrylates, vinylchloride, vinylidene chloride and acrylonitrile containing monomers.

For example, the latex polymers can be polymers or co-polymers of alkylacrylates, alkyl methacrylates, styrene, and vinyl acetate. Examples ofparticularly suitable latex polymers include Neocar™ 2300 and UCAR® 625(Dow Chemical Co., Midland, Mich.), and Airflex® EF811 (Air Products,Allentown, Pa.). Another monomer for copolymer production is ethylene,useful in the synthesis of ethylene-vinyl acetates.

A “reactive surfactant” is a molecule that typically has a longhydrophobic segment and a short ionizable and/or polar group. Unliketheir non-reactive counterparts, a reactive surfactant additionallycontains a reactive group on the hydrophobic segment that is capable ofcovalently bonding to the latex surface to facilitate curing andcrosslinking.

In an embodiment, the reactive surfactant used in the aqueous coatingcompositions of the invention comprises a polyglycerol ester and/or apolyglycerol ether of one or more unsaturated fatty acids. As usedherein, the phrase “polyglycerol ester and/or a polyglycerol ether ofone or more unsaturated fatty acids” is intended to refer to apolyglycerol ester of one or more unsaturated fatty acids and/or apolyglycerol ether of one or more unsaturated fatty acids.

As used herein, the term “polyglycerol” (used interchangeably hereinwith “polyglyceryl”) refers to “[o]ne of several mixtures of ethers ofglycerol with itself, ranging from diglycerol to triacontaglycerol.”Hawley's Condensed Chemical Dictionary, 14th Ed., John Wiley & Sons,Inc. (2002).

Examples of polyglycerols that can be used as part of the reactivesurfactant include diglycerol, triglycerol, tetraglycerol,pentaglycerol, hexaglycerol, heptaglycerol, octaglycerol, nonaglycerol,decaglycerol, pentadeca-glycerol and polyglycerols containing up to andincluding 30 repeat units of glycerol.

Polyglycerols can be produced by NaOH catalyzed condensation of glycerolat about 220° C. as disclosed by Linden & Lorient: “When hot and in thepresence of a catalyst, glycerol dehydration under vacuum results in amixture of polymerised glycerol.” Linden, G. and Lorient, D.,“Polyglycerol esters of fatty acids From Lipid chemistry—fatsubstitutes. New Ingredients in Food Processing,” pp. 297-298, WoodheadPublishing (1999).

As used herein, the term “degree of polymerization” refers to the numberof repeat units in an average polymer chain. The length is in monomerunits. The polyglycerols used in the ester and ether reactivesurfactants and humectants of the present invention can have a degree ofpolymerization of from about 2 to about 30. Each polyglycerol moleculecan be substituted at one hydroxyl group on average (monosubstituted),two hydroxyl groups on average (disubstituted), or at more positions onaverage.

The degree of polymerization of the polyglycerol derivative may also beindicated by the “hydroxyl value.” As used herein, the term “hydroxylnumber” refers to the number of free hydroxyl groups per monomer unit.

Polyglycerol derivatives of the invention can have a hydroxyl numberfrom about 0 to about 750. The molecular weight, hydroxyl number andhydroxyl value of selected polyglycerols are depicted in Table 1.

TABLE 1 Molecular Hydroxyl Hydroxyl Glycerol Derivative Weight NumberValue diglycerol 166 4 1352 triglycerol 240 5 1169 tetraglycerol 314 61071 pentaglycerol 388 7 1012 hexaglycerol 462 8 970 heptaglycerol 536 9941 octaglycerol 610 10 920 nonaglycerol 684 11 903 decaglycerol 758 12880 pentadeca-glycerol 1228 17 846

As used herein, the term “unsaturated” refers to “the state in which notall of the available valence bonds along an alkyl chain are satisfied.”Hawley's Condensed Chemical Dictionary, 1151, 14th Edition (2002, byJohn Wiley & Sons, Inc.).

As used herein, the term “fatty acid” refers to “a carboxylic acidderived from or contained in an animal or vegetable fat or oil.”Hawley's at p. 484.

The term “unsaturated fatty acids” encompasses polyunsaturated fattyacids. The unsaturated fatty acids, and particularly the polyunsaturatedfatty acids, may contain conjugated sites of unsaturation. Thepolyunsaturated fatty acids or derivatives thereof may have beenconverted to or naturally contain conjugated sites of unsaturation.

Unsaturated fatty acids that can be used to form the polyglycerol esterand/or ether derivative can be derived from a variety of sources. Forexample, the unsaturated fatty acids can be derived from an animal fator oil, a vegetable oil, a genetically modified vegetable oil, or achemically or enzymatically modified vegetable oil. Methods forobtaining fatty acids from animal fats or oils and vegetable oils arewell known in the art.

Useful animal fats and oils include any oil containing or comprisingunsaturated fatty acids, such as animal fat, beef tallow, borneo tallow,butterfat, cod-liver oil, herring oil, lanolin, lard, milk fat, mowrahfat, mutton tallow, neat's foot oil, pile herd oil, sardine oil, tallow,whale oil, and derivatives, conjugated derivatives, genetically-modifiedderivatives and mixtures thereof.

Other sources of suitable unsaturated fatty acids include used cookingoils, float grease from wastewater treatment plants, animal fats such asbeef tallow and pork lard, crude oils, “yellow grease,” i.e., animaloils and fats that have been used or generated as a result of thepreparation of food by a restaurant or other food establishment thatprepares or cooks food for human consumption with a free fatty acidcontent of less than 15%, and white grease, i.e., rendered fat derivedprimarily from pork, and/or other animal fats.

The vegetable oil from which the unsaturated fatty acids can be derivedis not particularly limited. For example, the vegetable oil can becamelina oil, canola oil, castor oil, cocoa butter, cocoa buttersubstitutes, coconut oil, coriander oil, corn oil, cottonseed oil, flaxoil, hazelnut oil, hempseed oil, jatropha oil, kokum butter, linseedoil, mango kernel oil, marine oils, meadowfoam oil, menhaden oil,mustard oil, olive oil, palm oil, palm kernel oil, palm kernel olein,palm kernel stearin, palm olein, palm stearin, peanut oil, phulwarabutter, pile herd oil, rapeseed oil, rice bran oil, safflower oil, salfat, sardine oil, sasanqua oil, shea fat, shea butter, soybean oil,sunflower seed oil, tall oil, tsubaki oil, tung oil, triacylglycerols,diacylglycerols, monoacylglycerols, triolein, triglycerides of mediumchain fatty acids, used cooking oils, yellow grease, other oils andderivatives, conjugated derivatives, genetically-modified derivatives ormixtures thereof.

For example, suitable vegetable oils include soybean oil, linseed oil,sunflower oil, corn oil, canola oil, rapeseed oil, cottonseed oil,peanut oil, tung oil, perilla oil, oiticica oil, castor oil, andsafflower oil. More particularly, the polyunsaturated fatty acid moietyis derived from soybean or linseed oil.

The term “genetically modified vegetable oil” refers to an oil derivedfrom a crop source that contains any gene alteration produced throughgenetic engineering techniques. Chemical or enzymatic modificationscomprise any alteration of the physical or chemical properties of anoil, such as level of saturation, conjugation, or epoxidation.

In an embodiment, the reactive surfactant comprising the polyglycerolderivative is a polyglycerol ester of one or more unsaturated fattyacids. As used herein, the term “ester” refers to being “derived from anacid by the exchange of the replaceable hydrogen of the latter for anorganic base.” Hawley's Condensed Chemical Dictionary, 14th Ed., p. 451,John Wiley & Sons, Inc. (2002).

Polyglycerol esters that can be used in aqueous coating compositions ofthe invention include those having formula I:

where in Formula I, n is preferably 2-30 and R′ is preferablysubstituted or unsubstituted, saturated or unsaturated alkyl, alkenyl,alkynyl, alkylaryl, arylalkyl or derivatives thereof, and where at leastone R is not H.

Alternatively, monochlorinated or monobrominated alkanes/alkenes or anepoxidized alpha olefin can react with polyglycerol to form esters.

The polyglycerol ester of an unsaturated fatty acid that can be used asa reactive surfactant in aqueous coating compositions of the inventionis not particularly limited. For example, the polyglycerol ester can beone or more compounds including, but not limited to, decaglycerolmonooleate, hexaglycerol monosoyate, diglyceryl monooleate, triglycerylmonooleate, tetraglyceryl monostearate, tetraglyceryl monooleate,decaglyceryl trioleate, decaglyceryl tristearate, decaglycerylpentaoleate, hexaglyceryl monolaurate, hexaglyceryl monococoate,hexaglyceryl monomyristate, decaglyceryl monolaurate, and decaglycerylmonomyristate.

For example, the term “decaglycerol monooleate” refers to a polyglycerolmonoester (i.e., decaglycerol) prepared from a mixture of fatty acidsenriched in oleic acid. A “monooleate” refers to a number ofpredominantly oleic fatty acid groups esterified to a polyglycerolmolecule varying around a central value of 1.

Similarly, the term “hexaglycerol monosoyate” refers to a polyglycerol(i.e. hexaglycerol) monoester prepared from the fatty acids typicallyfound in soybean oil, and includes such a monoester wherein theunsaturated fatty acid(s) are derived from soybean oil. A “monosoyate”refers to a number of acid groups esterified with a polyglycerolmolecule varying around a central value of 1.

The polyglycerol ester can also be polyglycerol monoesters of anunsaturated fatty acid derived from any of the fats and oils describedabove. Illustrative unsaturated fatty acids that can be esterified tothe polyglycerol include 4-decenoic acid, caproleic acid, 4-dodecenoicacid, 5-dodecenoic acid, lauroleic acid, 4-tetradecenoic acid,5-tetradecenoic acid, 9-tetradecenoic acid, palmitoleic acid,6-octadecenoic acid, oleic acid, 9-octadecenoic acid, 11-octadecenoicacid, 9-eicosenoic acid, cis-11-eicosenoic acid, cetoleic acid,13-docosenoic acid, 15-tetracosenoic acid, 17-hexacosenoic acid,6,9,12,15-hexadecatetraenoic acid, linoleic acid, linolenic acid (18:3n3), gamma linolenic acid (18:3 n6), β-eleostearic acid, gadoleic acid(20:1), β-eleostearic acid, punicic acid, 6,9,12,15-octadecatetraenoicacid, parinaric acid, 5,8,11,14-eicosatetraenoic acid, erucic acid,5,8,11,14,17-eicosapentaenoic acid (EPA), 7,10,13,16,19-docosapentaenoicacid, 4,7,10,13,16,19-docosahexaenoic acid (DHA), and the like.

Polyglycerol esters can be synthesized as disclosed in U.S. Pat. Nos.5,952,518 and 5,424,469, which are incorporated by reference herein.Polyglycerol esters can also be synthesized from polyglycerol and freefatty acids using a base catalyst or lipase as disclosed in U.S. Pat.No. 5,952,518.

Other well-known methods provided by Scrimgeour in “Chemistry of FattyAcids,” Bailey's Industrial Oil and Fat Products, Volume 1 page 12-13(6th Edition. Edited by: Shahidi, Fereidoon© 2005 John Wiley & Sons)include the well-known routes of synthesis of esters from alcohols (suchas polyglycerol and free fatty acids using an acid catalyst or alipase.) In addition, Bailey's discloses that the fatty acid or alcoholgroups present in an ester can be exchanged in a number of ways: byreaction with an excess of other fatty acids (acidolysis), alcohols(alcoholysis), or other esters (transesterification).

For example, conjugated linseed oils can be converted into fatty acidmethyl esters by transesterification with methanol. Conjugated linseedoil fatty acid methyl esters (CLOFAME) can be reacted with polyglycerolto produce polyglycerol esters with high levels of substitution.

Partial esters of polyglycerols (i.e., glycerol polymers wherein onlysome of the alcohols have been esterified) with C₈ to C₂₂ fatty acidsare also encompassed by the invention, and are generally prepared eithervia esterification of polyglycerols with corresponding saturated orunsaturated acids, or by trans-esterification of vegetable oils withpolyglycerols.

Illustrative commercial products that are particularly useful asreactive surfactants in aqueous coating compositions of the inventionare provided in Table 2 below.

TABLE 2 Suitable polyglycerol esters of unsaturated fatty acidsdiglyceryl monooleate NIKKO ® DGMO-90 triglyceryl monooleate DANISCOTS-T 122 tetraglyceryl monostearate NIKKO ® Tetraglyn 1-S tetraglycerylmonooleate NIKKO ® Tetraglyn 1-0 decaglyceryl trioleate NIKKO ® Decaglyn3-0 decaglyceryl tristearate NIKKO ® Decaglyn 3-S decaglycerylpentaoleate NIKKO ® Decaglyn 5-0 hexaglyceryl monolaurate NIKKO ®Hexaglyn 1-L hexaglyceryl monomyristate NIKKO ® Hexaglyn 1-Mdecaglyceryl monolaurate NIKKO ® Decaglyn 1-L decaglyceryl monomyristateNIKKO ® Decaglyn 1-M

In another embodiment of the invention, the polyglycerol derivative canbe a polyglycerol ether of one or more unsaturated fatty acids. As usedherein, the term “ether” refers to one of “a class of organic compoundsin which an oxygen atom is interposed between two carbon atoms in themolecular structure.” Hawley's, p. 453.

The polyglycerol ether of an unsaturated fatty acid for use in theaqueous coating compositions of the invention is not particularlylimited, and can be derived from any of the oils described above.

Examples of unsaturated fatty acids which can be linked to polyglycerolsthrough an ether bond to provide polyglycerol ethers useful for theinvention can include 4-decenoic acid, caproleic acid, 4-dodecenoicacid, 5-dodecenoic acid, lauroleic acid, 4-tetradecenoic acid,5-tetradecenoic acid, 9-tetradecenoic acid, palmitoleic acid,6-octadecenoic acid, oleic acid, 9-octadecenoic acid, 11-octadecenoicacid, 9-eicosenoic acid, cis-11-eicosenoic acid, cetoleic acid,13-docosenoic acid, 15-tetracosenoic acid, 17-hexacosenoic acid,6,9,12,15-hexadecatetraenoic acid, linoleic acid, linolenic acid (18:3n3), gamma linolenic acid (18:3 n6), β-eleostearic acid, gadoleic acid(20:1) β-eleostearic acid, punicic acid, 6,9,12,15-octadecatetraenoicacid, parinaric acid, 5,8,11,14-eicosatetraenoic acid, erucic acid,5,8,11,14,17-eicosapentaenoic acid (EPA), 7,10,13,16,19-docosapentaenoicacid, 4,7,10,13,16,19-docosahexaenoic acid (DHA), and the like.

Polyglycerol ethers can be synthesized as disclosed in U.S. Pat. No.2,258,892, which is incorporated by reference herein in its entirety.Partial ethers of polyglycerols (i.e., glycerol polymers wherein onlysome of the alcohols have been etherified) with C₈ to C₂₂ fattyalcohols, are also encompassed by the invention, and are generallyprepared via etherification of polyglycerols with fatty alcohols.Suitably, polyglycerols can also be etherified by fatty alcohols in thepresence of a reagent such as epichlorohydrin.

Additionally, the aqueous coating compositions of the invention canfurther comprise of one or more additives, fillers, dispersants,surfactants, thickeners, solvents, bases, defoamers, biocides, pigments,or any combination thereof.

Thickeners, also referred to as rheology modifiers, have several rolesin aqueous systems. They increase viscosity, maintain viscosity atrequired levels under specified processing conditions, provide improvedstability, pigment suspension and application properties. Suitablethickeners include natural thickeners, such as, for example, casein,alginates, xanthan gum, gum tragacanth, and modified celluloses, such asmethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose andcarbomethoxy cellulose; and synthetic thickeners, such as variousacrylic polymers, maleic anhydride copolymers, and polyethylenes.

Particularly suitable thickeners are reactive thickeners, as disclosedin U.S. Pat. No. 6,924,333, which is incorporated by reference in itsentirety. For example, the reactive thickener can include apolyunsaturated fatty acid or derivative thereof chemically attached topolyethylene glycol, or to an anionic or cellulosic water-solublepolymer. The anionic and cellulosic water-soluble polymers and thepolyunsaturated fatty acid or derivatives thereof disclosed in U.S. Pat.No. 6,924,333 are specifically contemplated herein.

Coalescent aids (or “coalescents”) have been used in coatings to soften,i.e., plasticize, the particulate polymers and facilitate the formationof a continuous film with optimum film properties once the water hasevaporated. In addition to increasing the ease of film formation,coalescent aids can also promote subsequent improvements in filmproperties by coalescing the particulate polymers and liquidpre-polymers and forming an integral film at ambient temperatures.

Coalescent aids are particularly helpful in assisting the formation ofparticulate polymer films possessing a high glass transitiontemperature, that is, the temperature which defines how easily theparticles of the polymer diffuse at the temperature at which thefilm-forming composition is applied. The presence of coalescent aids ina particulate polymer film having a high glass transition temperatureallows optimum film formation at ambient temperatures.

Illustrative coalescents include 2,2,4-Trimethyl-1,3-pentanediolMonoisobutyrate (TMB), available as Texanol™ ester alcohol (EastmanChemical Co., Kingsport, Tenn.), benzoate esters (Velate 368, VelsicolChemical Corporation, 10400 W. Higgins Road Suite 600, Rosemont, Ill.60018-3713, USA) and petroleum based low-VOC coalescents Optifilm 400and Optifilm 300—Eastman Chemical Co.; and phthalate plasticizersincluding dibutyl phthalate.

In an embodiment, aqueous coating compositions of the invention containa reactive coalescent, such as those disclosed in U.S. Appl. Publ. No.2004/0039095 A1, incorporated by reference in its entirety. For example,the reactive coalescent can be a glycol ester of an unsaturated fattyacid, particularly one which is derived from a vegetable oil, such as,for example, a propylene glycol monoester of vegetable oil fatty acids.Particularly suitable for use as a reactive coalescent is Archer RC™(ADM Specialty Oils & Fats, Decatur, Ill.), which contains corn oilpropylene glycol esters, predominantly propylene glycol monoesters ofcorn oil fatty acids (CAS Number 515152-38-2).

The dispersant can be composed of a polyunsaturated fatty acid moietychemically attached to a glycol, wherein the dispersant contains a freehydroxyl or a carboxyl group, as disclosed in U.S. Pat. No. 6,924,333.

An additional embodiment of the invention is directed to a method ofmaking an aqueous coating composition containing a reactive surfactant.The method comprises combining an aqueous latex film-forming polymerwith a reactive surfactant comprising one or more polyglycerolderivatives selected from the group consisting of a polyglycerol esterand a polyglycerol ether of one or more unsaturated fatty acids, asdescribed above. Methods of combining the polymer and the polyglycerolderivative to form the aqueous coating composition, along withoptionally one or more additives, fillers, dispersants, surfactants,thickeners, solvents, bases, defoamers, biocides, pigments, or anycombination thereof are well-known to those skilled in the art.

For example, if the coating composition is to be pigmented, at least onepigment can be dispersed in an aqueous medium under high shear such asis afforded by a COWLES® mixer or, in the alternative, at least onepre-dispersed pigment may be used. The emulsion polymer can be addedunder low shear stirring at the let down (completion) stage.

The polyglycerol esters and ethers of polyunsaturated fatty acids reduceor eliminate the need for traditional water-soluble additives that lowerthe water resistance of the dry coating (e.g. paint) film. Thesereactive surfactants can replace petroleum-based derivatives such asnonylphenol ethoxylates (NPEs), which have faced much scrutiny for theirlong term environmental impact on water supplies and aquatic life.

The polyglycerol esters and ethers of polyunsaturated fatty acids arecapable of oxidative crosslinking during the curing process, forming adry coating (e.g. paint) film that is more durable and water-resistantthan traditional latex compositions. Furthermore, these moieties havegood functionality, do not contribute to VOC, and can be advantageouslyused in conjunction with and interact with other polyunsaturatedcomponents in a latex formulation, such as reactive coalescents (e.g.,Archer RC™), reactive thickeners (see U.S. Pat. No. 6,924,333), andresins that include reactive sites such as acetoacetate functionality(i.e., having one or more acetoacetate groups), allowing for thebuilding of extended crosslinked networks (latent crosslinking) in latexpaints and other coatings.

Another embodiment of the invention is directed to aqueous coatingcompositions containing a humectant having a reduced VOC contentcompared to conventional humectants, such as ethylene glycol orpropylene glycol, which contribute to VOCs.

In one aspect, the aqueous coating composition comprises (a) one or morefilm-forming latex polymers and (b) a humectant comprising one or morepolyglycerols.

As used herein, the term “humectant” refers to a substance havingaffinity for water with stabilizing action on the water content of thematerial. A humectant keeps the moisture content caused by humidityfluctuations within a narrow range.

Polyglycerols that can be used in the aqueous coating compositions ofthe invention include those discussed above that are used as part of aderivative for the reactive surfactant, such as diglycerol, triglycerol,tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, octaglycerolnonaglycerol, decaglycerol, pentadeca-glycerol and polyglycerolscontaining up to and including about 30 repeat units of glycerol. Linearpolyglycerols are preferably used.

The polyglycerols that that are used as humectants in the aqueouscoating compositions of the invention can have a degree ofpolymerization of from about 2 to about 30.

The polyglycerol can be used in conjunction with a glycol such aspropylene glycol or ethylene glycol. For example, aqueous coatingcompositions of the invention can contain a ratio of the one or morepolyglycerols to a glycol, e.g. propylene glycol, of from about 1:99 toabout 99:1 by weight.

The amount of polyglycerol humectant that is used in the aqueous coatingcompositions of the invention is not particularly limited. Typically,the polyglycerol is used in an amount effective to achieve an open timeof about 5 to about 30 minutes, suitably from about 5 to about 15minutes, when the composition is applied to a substrate. For example,the one or more polyglycerols are present in an amount of from about 0.1to about 20% by weight of the composition.

The term “open time” refers to the time during which the aqueous coatingcomposition remains workable when applied to a surface. Typically,aqueous coating compositions (e.g. paints) have a sufficient amount ofopen time to re-brush or re-roll over a freshly coated wet surface toimprove its surface appearance or to apply additional paint onto thefreshly coated surface without causing such defects as brush marks, laplines resulting from differences in paint thickness, and loss of gloss.

Another embodiment of the current invention includes a method ofpreparing a humectant-containing aqueous coating composition. The methodcomprises combining an aqueous film-forming latex polymer with ahumectant comprising one or more polyglycerols. The one or morepolyglycerols are typically present in an amount effective to achieve anopen time of 5 to about 30 minutes, suitably from about 5 to about 15minutes, when the composition is applied to a substrate.

Isosorbide or a derivative thereof can also be used a humectant inaqueous coating compositions to provide suitable paint and coatingperformance with reduced VOC content compared to conventionalhumectants, such as propylene glycol. Accordingly, in anotherembodiment, the invention includes an aqueous coating compositioncomprising (a) one or more film-forming latex polymers and (b) ahumectant comprising isosorbide or a derivative thereof.

The term “isosorbide” refers to 1,4,3,6-dianhydrosorbitol, which isobtained by dehydration of sorbitol and therefore can be considered as avaluable product from biomass (Starch, Fleche, G. and Huchette, M.,38:1, 26-30 (1986)).

The term “isosorbide derivative” refers to esters and ethers ofisosorbide, ethoxylated isosorbides or polyglycerol esters ofisosorbide. Suitable derivatives of isosorbide include dimethylisosorbide, diacetyl isosorbide, and mixtures thereof.

The amount of isosorbide or derivative thereof used as a humectant inthe aqueous coating compositions of the invention is not particularlylimited. Typically, the polyglycerol is used in an amount effective toachieve an open time of about 5 to about 30 minutes, suitably from about5 to about 15 minutes, when the composition is applied to a substrate.For example, the isosorbide or derivative thereof is present in anamount of from about 0.1 to about 20% by weight of the composition.

Another embodiment of the current invention includes a method ofpreparing a humectant-containing aqueous coating composition. The methodcomprises combining an aqueous film-forming latex polymer with ahumectant comprising one or more of isosorbide or a derivative thereof.The one or more of isosorbide or a derivative thereof are typicallypresent in an amount typically in an amount effective to achieve an opentime of about 5 to about 30 minutes, suitably from about 5 to about 15minutes, when the composition is applied to a substrate.

Polyglycerols are polymers having an average molecular weight. Theycomprise a distribution with the number average identified as thecompound—hexaglycerol may comprise, for example, a mixture ofpolyglycerols ranging from diglycerol to octaglycerol: the averagemolecular weight would be that of hexaglycerol, and hexaglycerol wouldcomprise the preponderance of the mixture.

Polyglycerol, isosorbide, and/or isosorbide derivatives can be used toextend the open time of an aqueous coating composition. Thus, anotherembodiment of the invention includes a method for extending the opentime of an aqueous coating composition, comprising (a) forming anaqueous coating composition comprising at least one film-forming latexpolymer; and (b) combining with the coating composition a humectantselected from the group consisting of (i) one or more polyglycerols and(ii) one or more of isosorbide or a derivative thereof in an amounteffective to extend the open time of the coating composition. The opentime of the aqueous coating composition can be extended (compared to acomposition not containing a humectant) from about 5 minutes to about 30minutes, suitably from about 5 to about 15 minutes.

Additionally, the humectant-containing aqueous coating compositions ofthe invention can further comprise of one or more additives, fillers,dispersants, surfactants, thickeners, solvents, bases, defoamers,biocides, pigments, or any combination thereof, including all of thosedescribed in connection with the aqueous coating compositions comprisinga reactive surfactant, as described above.

The invention is also directed to a method for reducing the VOC contentof an aqueous coating composition comprising one or more film-forminglatex polymers and a humectant without substantially reducing open timeof the composition when applied to a substrate. The method comprisescombining the one or more film-forming latex polymers used in theaqueous coating composition with a humectant selected from the groupconsisting of (i) one or more polyglycerols and (ii) one or more ofisosorbide or a derivative thereof.

Polyglycerol, isosorbide, and derivatives of isosorbide can serve aszero-VOC humectants to help reduce levels of glycols such as propyleneglycol in latex paints and coatings without sacrificing control ofevaporation or maintenance of open time. Thus, in another embodiment,the invention is directed to a method for method for reducing the VOCcontent of an aqueous coating composition comprising one or morefilm-forming latex polymers and a humectant without substantiallyreducing open time of the composition when applied to a substrate. Themethod comprises combining the one or more film-forming latex polymersused in the aqueous coating composition with a humectant selected fromthe group consisting of (i) one or more polyglycerols and (ii) one ormore of isosorbide or a derivative thereof.

The aqueous coating compositions of the invention are particularlysuitable for coating substrates. Thus, in embodiments, methods of theinvention comprise providing an aqueous coating composition of theinvention (for example, a composition comprising one or morefilm-forming latex polymers and a reactive surfactant comprising one ormore polyglycerol derivatives chosen from a polyglycerol ester and apolyglycerol ether of one or more unsaturated fatty acids, or acomposition comprising a humectant such as polyglycerol, isosorbide, oran isosorbide derivative) and applying the composition to the substrate.

Methods of application of the aqueous compositions to a substrateinclude, but are not limited to, brushing, rolling, and spraying methodssuch as, for example, air-atomized spray, air-assisted spray, airlessspray, high volume low pressure spray, and air-assisted airless spray.

The aqueous compositions of the invention are particularly useful forand intended for application to a substrate, to produce articles ofmanufacture with the composition applied and coated thereto.Illustrative substrates to which the compositions of the invention canbe applied include wood, composites, textiles and nonwovens, paper,exterior siding, sheetrock, metal, plastics, cementitious substratessuch as, for example, concrete, stucco, and mortar, previously paintedor primed surfaces, and weathered surfaces and any other substrate forwhich a coating might be useful.

Although the aqueous compositions of the invention are particularlyuseful as coating compositions, they can also be used a variety of otherapplications, such as adhesives, polymers, inks, and in compositetechnology.

EXAMPLES Example 1 Synthesis of Conjugated Fatty Acid methyl esters

Highly reactive polyglycerol esters were synthesized from lineardecaglycerol (Brose Chemical Company, Twin Falls, Id.) and fatty acidmethyl esters of conjugated linseed oil (CLOFAME). Archer 1(Archer-Daniels-Midland Co., Decatur, Ill.) is a commercially availableCLOFAME.

Archer 1 (250 g), anhydrous methanol (200 mL, Aldrich) and sodiummethoxide (1.5 g, Aldrich) were added to a 1000 mL round bottom flaskand heated under reflux for 4 hours. The reaction mixture was thencooled to room temperature, poured into a separatory funnel, and allowedto separate into two layers. The lower glycerol and methanol layer wasremoved and the methyl ester layer was washed several times with hotwater to remove fatty acids. The methyl ester layer was dried overanhydrous MgSO₄ and filtered to give a clear amber liquid at roomtemperature.

Example 2 Synthesis of Reactive polyglycerol esters

Linear decaglycerol (10.0 g, Brose Chemical Company, Twin Falls, Id.)and CLOFAME from Example 1 (40.0 g) were added to a 4-neck round bottomflask equipped with an overhead stirring apparatus, Barret stylereceiver, condenser. The two starting materials formed a biphasicsystem. The reaction mixture was heated to 160° C. under a nitrogenpurge. At this temperature, anhydrous potassium carbonate (0.1 g) wasadded to the reaction. The reaction mixture was stirred for 4 hours at165° C. with mechanical stirring and a strong nitrogen purge. Thereaction was then cooled to room temperature and filtered. The resultingmaterial was a clear, amber monophasic viscous liquid at roomtemperature, soluble in hexane and insoluble in water, indicatingsubstantial esterification of polyglycerol with the fatty acids ofCLOFAME.

Example 3 Evaluation of Paint Formulations

The performance of paint formulations containing polyglycerol esterssuch as decaglycerol monooleate (MONO), hexaglycerol monosoyate anddecaglycerol monosoyate were compared with various nonyl phenylethoxylate (NPE) surfactants. Three formulations shown below usingNPE-based surfactants were replaced with Decaglycerol Monooleate (MONO)from Lonza (Basel, Switzerland) on a lb-lb basis. The MONO was dilutedwith 30% Propylene glycol for easy incorporation. Formulations I and IIwere evaluated with Archer RC™ while Formulation III was evaluated bothwith Archer RC™ and Texanol™ coalescents. Basic paint and filmproperties were evaluated with emphasis on water and alkali resistanceand color acceptance test.

TABLE 3 Types of Formulations Tested I. E-2252 Good Quality ExteriorFlat for Masonry (DOW) Tergitol ™ NP-9 II. E-2264 Exterior Semigloss(DOW) Triton ™ N-57 III. SGI-102 Low VOC Interior Semigloss (AirProducts) Triton ™ CF-10

TABLE 4 Formulation I.: E-2252 Good Quality Exterior Flat for MasonryRaw Materials lbs % gal Using HSD (high speed disperser - Stir Pak orHockmeyer) mix two ingredients under low speed (200-300 rpm) until HECis dissolved, about 15-20 minutes Water 199.90 24.05 Cellosize ™ HEC QP15,000 2.50 0.60 Add following ingredients one at a time while mixingunder low speed (200-300 rpm) about 5-10 minutes KTPP 2.00 0.25Nuosept ® 95 1.500 0.16 Rhodoline ® 643 2.00 0.28 Tergitol ™ NP-9 ¹ 3.000.34 AMP-95 1.00 0.13 Tamol ® 850 7.00 0.69 Add following pigments oneat a time under low speed (400-600 rpm). Continue mixing until uniform.Increase the speed (1000-1300 rpm) to completely disperse the pigmentsto 3-4 NS fineness of grind (FOG), about 45-60 minutes Ti-Pure ® R-902220.00 6.62 ZnO EPM-E 25.00 0.54 Snowflake ® CaCO3 100.00 4.45 Minex ® 4131.70 6.09 Pre-wet HEC with enough amount of water and immediately addto the mill base. Add remaining water and continue to disperse untiluniform with 3-4 NS fineness of grind (FOG), about 15 minutes Water127.10 15.29 Cellosize ™ HEC QP 15,000 2.30 0.55 Add followingingredients one at a time under medium speed (800- 1000 rpm) to completethe paint. Continue mixing to about 15 minutes Propylene Glycol 40.004.65 Rhodoline ® 643 2.00 0.28 Neocar ™ 2300 305.00 33.36 Coalescent13.00 1.65 Total 1185.00 100.00 Formulation Constant ² Archer RC ™Texanol ™ Formula, lb/gal 11.89 11.90 PVC 45.70 47.82 % TNV (wt - vol)56.46/38.71 55.37/37.02 VOC g/l 120.72 156.84 Paint Properties Standard³ Viscosity, Krebs/ICI 88-93 ku/0.8-1.0 p Gloss, 60°/85° 2/3 ScrubCycles ASTM with shim, >3000 Failure ¹ NPE replaced with DecaglycerolMonooleate (MONO) ² From Formulator ™V 4.3.86 IM (Color-Tec) ³ FromResin Supplier

TABLE 5 Formulation II: E-2264 Exterior Semigloss Raw Materials lbs %gal Using HSD (high speed disperser - Stir Pak or Hockmeyer) addfollowing ingredients one at a time while mixing under low speed(200-300 rpm), about 5-10 minutes Water 190.00 23.28 UCAR ® Polyphobe ®102 17.40 1.94 Ammonia Water 28% 1.80 0.24 Propylene Glycol 60.50 7.16Troysan ™ 586 1.80 0.2 Tamol ®1124 5.30 0.55 Rhodoline ® 643 1.80 0.26Triton ™ N-57 ¹ 2.10 0.25 Add following pigments one at a time under lowspeed (400-600 rpm). Continue mixing until uniform. Increase the speed(800-1200 rpm) to completely disperse the pigments to 5-6 NS fineness ofgrind (FOG), about 20-30 minutes Tronox ® CR-828 250.00 7.47 Polygloss ™90 25.00 1.18 Pre-mix the next two ingredients and add to above whilemixing under low speed (400-600 rpm), about 5-10 minutes Water 5.50 0.67UCAR ® Polyphobe ® 102 4.40 0.49 Add following ingredients one at a timeunder medium speed (600- 800 rpm) to complete the paint. Continue mixingto about 15 minutes Neocar ™ 2300 474.40 52.85 Rhodoline ® 643 1.80 0.26Coalescent 15.80 2.04 Polyphase ™ AF-1 7.40 0.79 Triton ™ GR-5M 1.180.13 Ammonia Water 28% 1.80 0.24 Total 1067.90 100.00 FormulationConstant ² Archer RC ™ Texanol ™ Formula, lb/gal 10.91 10.92 PVC 21.8223.06 % TNV (wt - vol) 52.79/39.60 51.31/37.51 VOC g/l 170.32 211.62Paint Properties Standard ³ Viscosity, Krebs/ICI 99 ku/1.5 p Gloss,60°/20° 59.5/19   ¹ NPE replaced with Decaglycerol Monooleate (MONO) ²From Formulator ™ V 4.3.86 IM (Color-Tec) ³ From Resin Supplier

TABLE 6 Formulation III. SGI-102 Low VOC Interior Semigloss RawMaterials lbs % gal Using HSD (high speed disperser - Stir Pak orHockmeyer) mix two ingredients under low speed (200-300 rpm) untilNatrosol ® Plus 330 is dissolved, about 15-20 minutes Water 100.00 11.98Natrosol ® Plus 330 3.00 0.26 Add following ingredients one at a timewhile mixing under low speed (200-300 rpm), about 5-10 minutes Water97.00 11.62 Tamol ® 1124 6.00 0.61 AMP-95 2.50 0.32 Strodex ® PK 90 2.000.21 Triton ™ CF-10 ¹ 2.00 0.22 Drewplus ™ L-475 1.50 0.20 Nuosept ® 951.50 0.16 Add following pigments one at a time under low speed (400-600rpm). Continue mixing until uniform. Increase the speed (800-1200 rpm)to completely disperse the pigments to 5-6 NS fineness of grind (FOG),about 45-60 minutes Tiona ® 596 230.00 6.80 Camel Wite 30.00 1.33Attagel ® 50 5.00 0.30 Add following ingredients one at a time undermedium speed (600- 800 rpm) to complete the paint. Continue mixing toabout 15 minutes Airflex ® EF811 228.00 25.52 UCAR ® 625 246.40 28.31Coalescent 13.00 1.64 Drewplus ™ L-475 3.00 0.39 Acrysol ® RM 2020NPR8.00 0.92 Acrysol ® RM-825 2.00 0.22 Water 75.00 8.98 Total 1055.9100.00 Formulation Constant ² Archer RC ™ Texanol ™ Formula, lb/gal10.55 10.56 PVC 22.91 24.00 % TNV (wt - vol) 50.90/37.93 49.67/36.24 VOCg/l 11.70 53.66 Paint Properties Standard ³ Viscosity, Krebs/ICI 96.0ku/0.90 p  Gloss, 60°/20° 47/11 Block Resistance ASTM 8 (VG) D4946 ¹ NPEreplaced with Decaglycerol Monooleate (MONO) ² From Formulator ™ V4.3.86 IM (Color-Tec) ³ From Resin Supplier

The formulations had the following properties as shown in Table 7.

TABLE 7 Paint Properties: Paint Properties E-2252 E-2264 SGI-102Exterior Flat for Masonry Exterior Semi-gloss Low VOC InteriorSemi-gloss Archer RC Archer RC Archer RC Archer RC Archer RC Archer RCTexanol Texanol + + + + + + + + MONO NPE MONO NPE MONO NPE MONO NPE Wetpaint rippling rippling rippling less rippling slight rippling smoothfilm finish rippling better tiny better wet rippling wet hide hideViscosity, 90.1 88.7 80.6 82.8 93.4 105 91.8 99.9 Krebs (ku) 0.763 0.7710.904 0.975 0.70 0.825 0.617 0.638 ICI (p) Gloss @ 20° 1.3 1.6 12.1 18.19.9 6.8 9.5 7.1 60° 2.5 2.5 52.5 62.6 44.1 38.6 44.4 39.8 85° 3.0 3.092.8 95.4 79.6 79.4 77.3 17.6 Opacity 94.85 95.5 96.65 97.64 96.9 97.5497.4 97.5 Color Acceptance¹ Rub Up Red Oxide dE = 0.43 dE = 0.42 dE =0.1  dE = 0.21 dE = 0.09 dE = 0.05 dE = 0.18 dE = 0.21 Thalo Blue dE =0.35 dE = 0.34 dE = 0.31 dE = 0.32 dE = 0.22 dE = 0.30 dE = 0.20 dE =0.41 Block Resistance² ASTM D4946 RT 1 day cure 9 10 0 0 0 2 8 8 3 daycure 10 10 9 3 4 −4 8 8 7 day cure 10 10 9 5 7 6 8 9 120° F. 1 day cure8 9 0 0 0 0 4 4 3 day cure 9 9 8 0 0 0 −4 5 7 day cure 10 10 9 1 6 5 6 6Heat-aged Stability 10 days 140° F. Gloss @ 20° 1.3 1.3 15.2 22 9.3 6.07.8 5.9 60° 2.6 2.4 56.6 64.9 43.1 36.0 40.9 36.9 85° 3.0 3.2 95.6 91.980.7 77.4 76.9 75.2 YE _(initial) 2.74 2.88 2.78 3.69 3.62 3.69 3.803.73 dYE 0.50 0.5 1.00 −0.08 0.11 0.18 −0.01 0.21 Scrub Cycles 30302210 >5200 >5200 1354 1510 1536 1348 with shim ASTM D2486 Alkali 4 4 3 44 4 4 4 Resistance³ 0.5% NaOH Water 4 4 4 4 4 5 4 5 Resistance³ Key forTable 7: ¹CIELab of Rub out portion with drawdown as standard ²10 =Perfect; 0 = Very Poor ³7 days immersion; 1 = Best ; 5 = Poor

For Formulation I, Both NPE and MONO based paint have same degree ofsurface imperfection. MONO gave a higher scrub resistance than NPE. Bothgave equal color acceptance; and block, water and alkali resistance.

For Formulation II, MONO gave more rippling and slightly lower glossthan NPE. MONO has better color acceptance with Red Oxide than NPE. NPEgave a very poor block (Rate=0) resistance while MONO was excellent(Rate=9). No difference from NPE was seen on its water and alkaliresistance.

For Formulation III, Archer RC™ and Texanol™ with MONO have better wethide than using NPE. Archer RC+MONO has less scrub than Texanol™+MONOand Archer RC™+NPE, while Archer RC™+MONO has improved scrub resistancethan Texanol™+NPE. NPE has better water resistance than MONO and equalalkali and block resistance.

Example 4 Performance of Paint Formulations Containing ReactiveSurfactants

Three samples were prepared containing reactive surfactants according tothe invention instead of NPEs. The samples were diluted with 30%Propylene Glycol for easy incorporation. Various properties of theformulations were evaluated.

TABLE 8 Formulation Ref: Modified SGI-102 Low VOC Interior Semigloss05-1201-2 Raw Materials Lbs % gal Using HSD (high speed disperser - StirPak or Hockmeyer) mix two ingredients under low speed (200-300 rpm)until Natrosol ® Plus 330 is dissolved, about 15-20 minutes Water 100.0011.98 Natrosol ® Plus 330 2.80 0.25 Add following ingredients one at atime while mixing under low speed (200-300 rpm), about 5-10 minutesWater 97.00 11.62 Tamol ® 1124 6.00 0.61 Ammonia Water 28% 2.50 0.33Strodex ® PK-90 2.00 0.21 Triton ™ GR 5M 2.00 0.23 Byk ® 1660 1.50 0.18Kathon ® LX 1.5% 1.50 0.18 Add following pigments one at a time underlow speed (400-600 rpm). Continue mixing until uniform. Increase thespeed (800-1200 rpm) to completely disperse the pigments to 5-6 NSfineness of grind (FOG), about 45-60 minutes Tiona ® 596 230.00 6.80Camel Wite 30.00 1.33 Attagel ® 50 5.00 0.3 Add following ingredientsone at a time under medium speed (600- 800 rpm) to complete the paint.Continue mixing to about 15 minutes Water 50.00 5.99 Airflex ® EF811218.00 24.41 UCAR ® 625 240.00 27.59 Archer RC ™ 10.00 1.32 Byk ® 16603.00 0.36 Acrysol ®RM 2020NPR 8.00 0.92 Acrysol ® RM-825 1.90 0.21 Water43.35 5.19 Total 1054.55 100.00 Formulation Constants VOC g/l 13.23 %TNV (wt-vol) 49.81-36.45 Formula, lbs/gal 10.55 PVC 23.82

The formulations had the following properties as shown in Table 9.

TABLE 9 Paint Properties: Standard Decaglycerol HexaglycerolDecaglycerol Without Properties GR 5M Monooleate Monosoyate MonosoyatePK 90 Wet paint film finish Smooth Smooth Smooth Smooth SmoothViscosity, Krebs (ku) 94.3 81.5 82.20 83.0 81.50 ICI (p) 0.542 0.5290.50 0.508 0.479 Gloss @ 85° 74.9 79.60 80.60 77.80 76.90 60° 38.3 48.1047.40 47.90 46.70 20° 6.3 10.50 10.30 10.50 76.90 Opacity 96.4 96.3096.20 96.40 96.25 Color Acceptance¹ Rub Up Red Oxide dE = 0.10 dE = 0.12dE = 0.18 dE = 0.16 dE = 0.22 Thalo Blue dE = 0.25 dE = 0.30 dE = 0.33dE = 0.36 dE = 0.35 Block Resistance² ASTM D4946 RT 1 day cure −8 9 9 98 3 day cure 8 8 9 9 5 7 day cure 8 8 9 9 3 120° F. 1 day cure −7 8 7 70 3 day cure −8 8 8 8 0 7 day cure 8 8 8 8 0 Freeze-Thaw Failed FailedFailed Failed Failed ASTM D2243 Cycle 1 Scrub Cycles 921 930 922 890 900ASTM D2486 Alkali Resistance³ 1 1 2 4 3 (5% NaOH) Water Resistance³ Nochange No change No change No change No change ¹CIELab of Rub outportion with drawdown as standard ²10 = Perfect; 0 = Very Poor ³7 daysimmersion; 1 = Best; 5 = Poor

Results:

All three samples gave higher gloss than standard NPE containingformulations.

Hexaglycerol and Decaglycerol monosoyate gave better block at roomtemperature. Standard and Mono gave the best alkali resistance followedby Hexaglycerol. There was not much difference on the color acceptanceand scrub resistance.

Example 5 Evaluation of Polyglycerol with Propylene Glycol in a PaintFormulation

Linear decaglycerol (Brose Chemical Company, Twin falls, Id.) was usedas a humectant to replace Propylene Glycol to decrease VOC in latexpaint and increase open time to a sufficient level.

TABLE 10 Method: 1. Linear decaglycerol was diluted with 25% water foreasy incorporation. 2. Formulation used was a semigloss paint. 3.Propylene Glycol was replaced with Linear decaglycerol as follows: a.100% replacement b. 3 parts Propylene Glycol: 1 part Polyglycerol c. 1part Propylene Glycol: 1 part Polyglycerol d. 1 part Propylene Glycol: 3parts Polyglycerol 4. Various properties were compared.

TABLE 11 Paint Formulation-ADM 30-1011 Raw Materials 3 Parts 1 part 1Part 1 Part 1 Part 1 Part PG PG PG PG PG PG 100 % 1 part 1 Part 3 Parts3 Parts 3 Parts 3 Parts 1 part PG PolyG PolyG PolyG PolyG PolyG PolyG 1PolyG Standard 05-1565-1 05-1565-2 05-1565-3 05-1565-4 05-1565-505-1565-6 05-1565-7 lbs gal lbs Lbs lbs lbs lbs lbs lbs Using HSD (highspeed disperser-StirPak or Hockmeyer) add following ingredients one at atime while mixing under lowspeed (200-300 rpm), about 3-5 minutes Water70.00 8.39 70.00 70.00 70.00 70.00 70.00 70.00 70.00 Kathon ® 1.75 0.211.75 1.75 1.75 1.75 1.75 1.75 1.75 LX 1.5% Propylene 12.00 1.39 — 9.006.00 3.00 3.00 3.00 3.00 Glycol Linear 12.00 3.00 6.00 9.00 9.00 9.009.00 decaglycerol Tamol ® 5.00 0.51 5.00 5.00 5.00 5.00 2.50 2.50 2.501124 Add the pigment slowly. Continue mixing until uniform. Increase thespeed (800-1200 rpm) to completely disperse the pigments to 5-6 finenessof grind (FOG), about 15-20 minutes. Omyacarb ® 165.00 7.31 165.00165.00 165.00 165.00 165.00 165.00 165.00 UF Add under low speed andcontinue mixing till uniform ( 300-600 rpm), about 10 Minutes Kronos ®260.00 13.33 260.00 260.00 260.00 260.00 260.00 260.00 260.00 4311Slurry Add following ingredients one at a time under medium speed(600-800 rpm) to omptete the paint. Continue mixing to about 15 minutes.Water 60.00 7.19 60.00 60.00 60.00 60.00 60.00 60.00 60.00 Rhoplex ®440.00 51.18 440.00 440.00 440.00 440.00 440.00 440.00 440.00 SG-30Archer RC ™ 11.27 1.48 11.27 11.27 11.27 11.27 11.27 11.27 11.27Aerosol ® 1.50 0.16 1.50 1.50 1.50 1.50 1.50 0.75 0.00 OT-75 Byk ® 16602.06 0.24 2.06 2.06 2.06 2.06 2.06 2.06 2.06 Ammonia 1.50 0.20 1.50 1.501.50 1.50 1.50 1.50 1.50 Water 28% Acrysol ® 16.00 1.84 16.00 16.0016.00 16.00 16.00 16.00 16.00 2020NPR Acrysol ® 6.00 0.70 6.00 6.00 6.006.00 6.00 6.00 6.00 SCT-275 Water 48.98 5.87 48.98 48.98 48.98 48.9850.55 51.28 51.98 Total 1101.06 100.00 1101.06 1101.06 1101.06 1101.061100.13 1100.11 1100.06 Formulation Constant VOC (g/l) 48.06 14.04 39.5531.05 22.54 22.60 22.62 22.64 Lbs/gal 11.01 11.00 11.01 11.01 11.0111.00 11.00 11.00 % Solids by 54.84 55.94 55.12 55.39 55.67 55.58 55.5355.48 weight % Solids by 40.26 41.67 40.61 40.97 41.32 41.21 41.15 41.09volume PVC 33.06 31.94 32.77 32.49 32.21 32.30 32.35 32.39

The formulations had the following properties, as shown in Table 12.

TABLE 12 Paint Properties Properties 3 Parts 1 part 1 Part 1 Part 1 Part1 Part PG PG PG PG PG PG Standard 100% 1 part 1 Part 3 Parts 3 Parts 3Parts 3 Parts 1 part PolyG PolyG PolyG PolyG PolyG PolyG PolyG PG05-1565-1 05-1565-2 05-1565-3 05-1565-4 05-1565-5 05-1565-6 05-1565-7Viscosity, ku 103 106.5 103.8 104.3 105.2 108 111 119.4 Viscosity, ku112.6 112.6 113.7 111.8 115.8 after overnight pH 9.04 9.0 9.02 9.06 9.059.05 9.08 9.05 Opacity 96.11 96.74 96.44 96 96.25 95.90 95.35 96.50Gloss g @ 20 deg 3.2 4.6 3.6 4.0 4.2 3.5 3.6 3.7 60 deg 23.4 30.5 26.627.6 28.5 24.10 24.9 24.7 85 deg 73.5 80.1 77.0 75.4 78.5 72.60 73.573.3 VOC g/l 48.06 14.04 39.55 31.05 22.54 N/A N/A N/A Reduction; 70% 17%  35% 53% Open Time¹, min No line mark 1 1 1 2 2 N/A N/A N/A Heavyline mark 4 4 4 5 6 Sag, ASM-3 mils 18 18 16 18 18 N/A N/A N/A Rating (1= best) 2 4 5 3 1 Block Resistance² ASTM D4946 RT 1-day 9 8 9 8 8 9 9 93-day 9 9 9 9 9 9 9 9 7-day 10 10 10 10 10 10 10 10 120° F. 1-day 2 0 10 0 1 3 4 3-day 4 3 5 4 5 3 4 5 7-day 9 8 8 8 8 9 9 9 Alkali 3 5 2 4 1Very Very Very Resistance³ poor poor poor (5% NaOH) with with with noblisters; only efflore efflore efflores yellowish scense scense censemapping; with capillary action Water³ (no blisters; All All All All AllNo No No no yellowish equal equal equal equal equal change change changemapping; with (Best) capillary action) Scrub Cycles 1900 1.500 1700 18001575 1481 1385 1404 ASTM 21% 10.5% 5.3% 17% D2486 (% decrease) ¹Resinvendor in-house test procedure ²10 = Perfect ; 0 = Very Poor ³7 daysimmersion 1 = Best ; 5 = Poor

Results: Polyglycerol, at 100% replacement, decreased scrub and blockresistance at elevated temperatures and gave poor alkali resistance. Ablend of 1 part Propylene Glycol and 3 parts Polyglycerol gave betteropen time, sag at 18 mils, and alkali resistance than the standard.

Decreasing the amount of surfactants and dispersant in the formulation,with 1 part Propylene Glycol and 3 parts Polyglycerol, improved theblock resistance, but decreased scrub and gave a very poor alkaliresistance.

Example 6 Evaluation of an Isosorbide Paint Formulation

Isosorbide was evaluated in Low VOC (<50 g/l) formulations, ADM 30-1011Low Sheen Interior/Exterior White and ADM 11-1011 High GlossInterior/Exterior White (with good adhesion to aged alkyd). Theisosorbide sample was diluted with water at a 1:1 ratio by weight andwas evaluated versus Propylene Glycol on a lb-lb basis. Basic paintproperties were evaluated for baseline comparison.

TABLE 13A Isosorbide Paint Formulation 1. Formulation constants werefrom Formulator ™ V 4.3.86 IM (Color-Tec) ADM 30-1011 Low SheenInterior/Exterior White lbs gallons Using HSD (high speed disperser-StirPak or Hockmeyer) add following ingredients one at a time whilemixing under low speed (200-300 rpm), about 3-5 minutes Water 70.00 8.40Kathon LX 1.5% 1.75 0.21 Tamol 1124 5.00 0.51 Add the pigment slowly.Continue mixing until uniform. Increase the speed (800-1200 rpm) tocompletely disperse the pigments to 5-6 fineness of grind (FOG), about15-20 minutes Omyacarb UF 165.00 7.31 Add under low speed and continuemixing till uniform (300-600 rpm), about 10 minutes Titanium Dioxide260.00 13.33 Kronos ® Slurry 4311 Add following ingredients one at atime under medium speed (600- 800 rpm) to complete the paint. Continuemixing to about 15 minutes. Propylene Glycol 12.00 1.39 Rhoplex SG-30440.00 51.18 Water 60.00 7.20 Aerosol OT-75 1.50 0.16 Archer RC 11.271.48 Byk 1660 2.06 0.24 Ammonia Water 28% 1.50 0.20 Acrysol SCT-75 6.000.70 Acrysol RM 2020NPR 16.00 1.84 Water 48.64 5.84 Total 1100.72 100.00Formulation Constants VOC g/l 48.06 Coalescent on Resin 5.12% solid %Weight Solids 54.84 % Volume Solids 40.26 PVC 33.06

TABLE 13B Isosorbide Paint Formulation 2. Formulation constants werefrom Formulator ™ V 4.3.86 IM (Color-Tec) ADM 11-1011 High GlossInterior/Exterior White Raw Materials lbs gallons Using HSD (high speeddisperser -StirPak or Hockmeyer) add following ingredients one at a timewhile mixing under low speed (200-300 rpm), about 3-5 minutes Water70.00 8.40 Kathon LX 1.5% 1.60 0.19 Tamol 2001 2.70 0.30 Byk 022 1.000.12 AMP 95 0.50 0.06 Add the pigments slowly. Continue mixing untiluniform. Increase the speed (800-1200 rpm) to completely disperse thepigments to 5-6 fineness of grind (FOG), about 15-20 minutes TitaniumDioxide R-706 225.00 6.66 Polygloss 90 10.00 0.46 Add followingingredients one at a time under medium speed (600- 800 rpm) to completethe paint. Continue mixing to about 15-20 minutes. Propylene Glycol 7.750.90 Rhoplex HG-700 600.00 67.82 Water 21.45 2.57 Triton X-405 2.30 0.25Archer RC 10.00 1.32 Texanol 8.00 1.01 Water 22.00 2.64 Acrysol RM2020NPR 14.00 1.61 Acrysol RM 8W 3.00 0.34 Byk 024 2.00 0.24 Water 42.475.10 Total 1043.77 100.00 Formulation Constants VOC g/l 49.55 Coalescenton Resin solid % 6.67 % Weight Solids 50.19 % Volume Solids 37.51 PVC18.97

The properties of the paint formulations are provided in Table 14,below.

TABLE 14 Properties of isosorbide paint formulations ADM 30-1011 LowSheen ADM 11-1011 High Gloss Interior/Exterior White Interior/ExteriorWhite Propylene Propylene Isosorbide Glycol Isosorbide Glycol Viscosity,ku 100.9 104.6 100.6 100 Opacity Y 96.55 96.91 96.76 97.08 black Y 87.4088.12 88.44 89.07 white 90.52 90.93 91.40 91.75 Yellowing Index L 96.3896.36 96.81 96.81 a −1.36 −1.37 −1.44 −1.45 b 1.49 1.47 1.69 1.68 YE2.15 2.12 2.45 2.43 Gloss @ 60 deg 25.8 21 75.9 75.2 Color Acceptance¹CIELab No rub up No rub up No rub up No rub up Red Oxide da* 0.15 0.210.16 0.13 dE* 0.192 0.25 0.233 0.194 Thalo Blue db* 0.34 0.19 0.10 0.15dE* 0.477 0.303 0.186 0.255 LTC With tiny cracks passed With 1-2 tinypassed on edges on cracks on edges on unsealed portion unsealed portionBlock 1 - day 0 1 9 9 3 - day 2 4 9 9 7 - day 5 6 10 10 Open Time² WetApplication Better Better brushability brushability Sharp mark @ 4 4 4 2Starts to be sticky @ 6 5 6 4 Stopped @ 7 6 7 5 After overnight dry Nomark @ 1 1 1 with mark at 1 Sharp mark @ 3 2 3 2 Heat-aged StabilityIn-can Very slight Very slight No syneresis, No syneresis, conditionsyneresis syneresis creamy on top creamy on top Viscosity, ku +5.70 +2−3.40 −3.00 Gloss @ 60 deg +2.2 +1.1 +2.0 +1.2 Yellowing Index, dYE 0.500.48 0.50 0.51 Freeze-thaw Cycle 1 Cottage Cottage 140.2 ku 139.2 kuCycle 2 cheese but Cheese 140.2 ku 134.5 ku Cycle 3 softer than 140.2 ku135.6 ku PGlycol Adhesion to aged gloss alkyd 1 day curing N/A N/A1-coat 1B 48% 3B 10% removal removal 2-coats 1B 56% 2B 24% removalremoval 7 day curing 1-coat 4B <5% 4B <5% removal removal 2-coats 4B <5%4B <5% removal removal Scrub Resistance, 2085 1750 573 720 cycles failed¹Standard - Unrubbed Portion; Sample - Rubbed Portion ²Emulsion VendorIn-house Procedure

Low temperature coalescing (LTC) of isosorbide paints in bothformulations showed very tiny cracks on edges of unsealed portion of thePenopac paper which were not present with Propylene Glycol. However,paint containing isosorbide gave better scrub resistance but inferiorblock in Low Sheen Formulation. In both formulations, paint containingisosorbide gave higher gloss, better freeze-thaw resistance and betteropen time than Propylene Glycol. Adhesion to aged gloss alkyd surface at1 day curing was not as good as Propylene Glycol but was better at 7-daycuring, as shown in FIG. 1.

Based on the result of the evaluations, isosorbide can be used toimprove the ease of application of the paint, open time and freeze-thawresistance. Isosorbide gave better scrub resistance in bothformulations, and also gave higher gloss, better freeze-thaw resistanceand better open time than Propylene Glycol.

TABLE 15 Raw Material Suppliers referenced by Examples Raw MaterialsFunction Supplier Acrysol ® RM-825 Rheology modifier, Rohm and HaasUrethane based Acrysol ® SCT-275 Rheology modifier, Rohm and HaasUrethane based Acrysol ®RM Rheology modifier, Rohm and Haas 2020NPRUrethane based Acrysol ®RM 8W Rheology modifier, Rohm and Haas Urethanebased Aerosol ® OT-75 Surfactant Cytec Airflex ® EF811 Emulsion, VinylAir Products Acetate Ethylene Ammonia 28% Neutralizer Various AmmoniaWater 28% Neutralizer Various AMP-95 Neutralizer DOW Archer RC ™Coalescent Archer Daniels Midland Co. Attagel ® 50 Rheology modifier,Engelhard Attapulgite Byk ® 022 Defoamer Byk-Chemie Byk ® 024 DefoamerByk-Chemie Byk ® 1660 Defoamer Byk-Chemie Byk ® 1660 Defoamer Byk-ChemieCamel Wite Extending Pigment, Imerys Calcium Carbonate Cellosize ™ HECQP Rheology modifier, DOW 15,000 Hydroxyethylcellulose Drewplus ™ L-475Defoamer Drew Chemicals Kathon ® LX 1.5% In-can preservative Rohm andHaas Kronos ® Slurry 4311 Hiding Pigment Kronos (76 ± 1% TitaniumDioxide in water) KTPP, Potassium Dispersant Astaris TripolyphosphateMinex ® 4 Extending Pigment, Unimin Nepheline Syenite Natrosol ® Plus330 Rheology modifier, Hercules Modified Hydroxyethylcellulose Neocar ™2300 Emulsion, Acrylic DOW In-can preservative Nuodex Omyacarb ® UFExtending Pigment, Omya Calcium Carbonate Polygloss ™ 90 Extendingpigment, Huber Kaolin Clay Linear decaglycerol Humectant Brose ChemicalCompany Polyphase ™ AF-1 Film preservative Troy Chemicals PropyleneGlycol Cosolvent Various Rhodoline ® 643 Defoamer Rhodia Rhoplex ®HG-700 Emulsion, Self- Rohm and Haas crosslinking Acrylic Rhoplex ®SG-30 Emulsion, Acrylic Rohm and Haas Snowflake ® CaCO3 ExtendingPigment, Imerys Calcium Carbonate Strodex ® PK-90 Surfactant DexterChemicals Tamol ® 2001 Dispersant Rohm and Haas Tamol ® 1124 DispersantRohm and Haas Tamol ® 850 Dispersant Rohm and Haas Tergitol ™ NP-9Surfactant, DOW NPE-based Texanol ™ Coalescent Eastman Tiona ® 596Hiding Pigment, Millenium Titanium Dioxide Chemicals Ti-Pure ® R-902Hiding Pigment, Dupont Titanium Dioxide Ti-Pure ® R-706 Hiding Pigment,Dupont Titanium Dioxide Triton ™ CF-10 Surfactant, DOW NPE BasedTriton ™ GR-5M Surfactant DOW Triton ™ N-57 Surfactant, DOW NPE BasedTriton ™ X-405 Surfactant DOW Tronox ® CR-828 Hiding Pigment, Kerr-McgeeTitanium Dioxide Troysan ™ 586 In-can preservative Troy Chemicals UCAR ®625 Emulsion, Acrylic DOW UCAR ® Polyphobe ® 102 Rheology modifier, DOWUrethane-alkali swellable ZnO EPM-E Zinc Oxide Film Umicore preservative

Having now fully described this invention, it will be understood tothose of ordinary skill in the art that the same can be performed withina wide and equivalent range of conditions, formulations, and otherparameters without affecting the scope of the invention or anyembodiment thereof.

All documents, e.g., scientific publications, patents, patentapplications and patent publications, if cited herein are herebyincorporated by reference in their entirety to the same extent as ifeach individual document was specifically and individually indicated tobe incorporated by reference in its entirety. Where the document citedonly provides the first page of the document, the entire document isintended, including the remaining pages of the document.

1. An aqueous coating composition comprising: (a) one or morefilm-forming latex polymers, and (b) a humectant comprising one or moreof isosorbide or a derivative thereof.
 2. The composition of claim 1,wherein the isosorbide or a derivative thereof is present in an amounteffective to achieve an open time of about 5 to about 30 minutes whenthe composition is applied to a substrate.
 3. The composition of claim1, wherein the humectant is selected from the group consisting ofisosorbide, dimethyl isosorbide, diacetyl isosorbide, and mixturesthereof.
 4. The composition of claim 1, further comprising one or moreadditives, fillers, dispersants, surfactants, thickeners, solvents,bases, defoamers, biocides, or pigments.
 5. A method of coating asubstrate, comprising providing the aqueous coating composition of claim1 and applying the composition to the substrate.
 6. A substrate havingthe composition of claim 1 applied thereto.
 7. An article of manufacturecomprising the coated substrate of claim
 6. 8. A method for extendingthe open time of an aqueous coating composition, comprising: (a) formingan aqueous coating composition comprising at least one film-forminglatex polymer; and (b) combining with the coating composition ahumectant selected from the group consisting of: (i) one or morepolyglycerols; and (ii) one or more of isosorbide or a derivativethereof, in an amount effective to extend the open time of the coatingcomposition.
 9. The method of claim 8, wherein the open time of thecomposition is from about 5 minutes to about 30 minutes, suitably fromabout 5 to about 15 minutes.
 10. The method of claim 8, wherein the opentime of the composition is from about 5 minutes to about 15 minutes. 11.A method for reducing the VOC content of an aqueous coating compositioncomprising one or more film-forming latex polymers and a humectantwithout substantially reducing open time of the composition when appliedto a substrate, comprising combining the one or more film-forming latexpolymers used in the aqueous coating composition with a humectantselected from the group consisting of: (i) one or more polyglycerols;and (ii) one or more of isosorbide or a derivative thereof.